JP4273387B2 - Detoxification treatment method for halogen-containing resin - Google Patents
Detoxification treatment method for halogen-containing resin Download PDFInfo
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- JP4273387B2 JP4273387B2 JP2002298589A JP2002298589A JP4273387B2 JP 4273387 B2 JP4273387 B2 JP 4273387B2 JP 2002298589 A JP2002298589 A JP 2002298589A JP 2002298589 A JP2002298589 A JP 2002298589A JP 4273387 B2 JP4273387 B2 JP 4273387B2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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Description
【０００１】
【発明の属する技術分野】
本発明は、ハロゲン含有樹脂の無害化処理方法に関し、特に、塩化ビニル樹脂などを、ダイオキシンを発生させることなく処理できるハロゲン含有樹脂の無害化処理方法に関する。
【０００２】
【従来の技術】
近年、農業用ビニルハウスに使用したシートやゴミ袋が大量に廃棄されている。
【０００３】
これらのシートやゴミ袋には、軟質塩化ビニル樹脂が一般的に使用されているが、軟質塩化ビニル樹脂などの塩化ビニル樹脂をそのまま焼却すると、猛毒のダイオキシンが発生する。
【０００４】
したがって、現状では、農業用ビニルハウスに使用した軟質塩化ビニル樹脂のシートは、倉庫に保管するか、空き地、山地、農地に山積みするかされている。
【０００５】
【発明が解決しようとする課題】
本発明は、上記問題を解決すべく成されたもので、使用済みの軟質塩化ビニル樹脂シートなどのハロゲン含有樹脂を、ダイオキシンを発生させることなく、しかも安価に処理できるハロゲン含有樹脂の無害化処理方法を提供することを目的とする。
【０００６】
【課題を解決するための手段】
請求項１に記載の発明は、ハロゲン含有樹脂を溶融させ、石膏類のみ、または石膏類および非揮発製油のみと混合して４００〜８００℃の温度で焼却することを特徴とするハロゲン含有樹脂の無害化処理方法に関する。
【０００７】
塩化ビニル樹脂などのハロゲン含有樹脂を空気中で燃焼させると、熱分解により、ハロゲン含有樹脂中のハロゲン原子、たとえば塩素原子と、ハロゲン含有樹脂中の炭素原子および水素原子と、空気中の酸素原子とからダイオキシンが発生する。
【０００８】
しかしながら、前記ハロゲン含有樹脂の無害化処理方法においては、ハロゲン含有樹脂を石膏類の存在下で加熱している。ここで、石膏類は、硫酸カルシウムを主成分として含有しているから、前記ハロゲン含有樹脂中のハロゲンは、全て前記石膏類中の硫酸カルシウムと反応して固定される。したがってダイオキシンが生成することが防止される。
【００１０】
前記ハロゲン含有樹脂の無害化処理方法においては、ハロゲン含有樹脂と石膏類との反応温度を前記温度範囲に設定しているから、ハロゲン含有樹脂に含まれるハロゲン原子は全て石膏類と反応する。したがって、ダイオキシンの発生防止効果が特に高い。また、反応温度が８００℃以下と比較的低温であるから、通常の焼却炉を用いて処理した場合に、焼却炉が損傷することが殆どない点でも好ましい。
【００１１】
請求項２に記載の発明は、石膏類の割合が、ハロゲン含有樹脂と石膏類との合計量を１００重量部としたとき、５〜３０重量部であるハロゲン含有樹脂の無害化処理方法に関する。
【００１２】
本発明のハロゲン含有樹脂の無害化処理方法においては、石膏類の割合が５重量部以上であれば、ハロゲン含有樹脂中のハロゲン原子は石膏類と全て反応する。また、石膏類の割合が３０重量部以下であれば、固形残滓が大量に発生することもない。前記請求項にかかる発明は、このような知見に基づいている。
【００１３】
請求項３に記載の発明は、ハロゲン含有樹脂と石膏類のみ、またはハロゲン含有樹脂と石膏類と非揮発性油のみを混合して焼却することにより、両者を反応させる請求項１または２に記載のハロゲン含有樹脂の無害化処理方法に関する。
【００１４】
前記ハロゲン含有樹脂の無害化処理方法は、たとえば、ハロゲン含有樹脂と石膏類とを混合して豆炭状に成形し、これを焼却炉で焼却することにより、容易に実施できる。
【００１６】
前記ハロゲン含有樹脂の無害化処理方法は、請求項４に記載のハロゲン含有樹脂の無害化処理方法において、ハロゲン含有樹脂を溶融させて石膏類と混合する例である。
【００１７】
この無害化処理方法によれば、ハロゲン含有樹脂と石膏類とを均一に混合できるから、ハロゲン含有樹脂を処理する際のダイオキシンの発生をより効果的に防止できる。
【００１８】
また、前記無害化処理方法は、ハロゲン含有樹脂が塩化ビニル樹脂のように熱可塑性である場合に好適に実施できる。
【００２０】
前記無害化処理方法においては、ハロゲン含有樹脂を石膏類と均一に混合でき、また、ハロゲン含有樹脂を前記非揮発性油に溶解させることができるのであれば、ハロゲン含有樹脂を熱溶解させる必要がない。本方法は、特に、前記ハロゲン含有樹脂が非揮発性油に溶解する場合に好適に実施できる。
【００２１】
請求項４に記載の発明は、前記石膏類が、硫酸カルシウム、結晶石膏、半水石膏、無水石膏、石膏プラスタ、無水石膏プラスタ、および硬石膏プラスタからなる群から選択されてなるハロゲン含有樹脂の無害化処理方法に関する。
【００２２】
前記結晶石膏、半水石膏、無水石膏、石膏プラスタ、無水石膏プラスタ、および硬石膏プラスタの何れにも、不純物として酸化カルシウムが相当量含まれている。したがって、ハロゲン含有樹脂中のハロゲンが前記結晶石膏等に含まれる硫酸カルシウムと反応して生成した硫酸は、前記酸化カルシウムと反応して固定されると考えられるから、前記ハロゲンの固定が特に円滑に行われる。
【００２３】
請求項５に記載の発明は、前記ハロゲン含有樹脂が、熱可塑性を有するハロゲン含有熱可塑性樹脂および熱硬化性を有するハロゲン含有熱硬化性樹脂から選択された少なくとも１種の樹脂であるハロゲン含有樹脂の無害化処理方法に関する。
【００２４】
請求項８は、本発明の無害化処理方法が、後述する塩化ビニル系樹脂のようなハロゲン含有熱可塑性樹脂だけでなく、骨格中にハロゲン原子を含有するエポキシ樹脂のような熱硬化性樹脂にも適用できることを明確にした請求項である。
【００２５】
請求項６に記載の発明は、前記ハロゲン含有熱可塑性樹脂が、ハロゲン基を有するハロゲン化ビニル化合物の単独重合体または共重合体であるハロゲン化ビニル系樹脂、並びにハロゲン基を有しないビニルモノマーを重合して得られるハロゲン非含有ビニル系樹脂にハロゲン系難燃剤を配合してなる難燃化ビニル系樹脂からなる群から選択された少なくとも１種の樹脂であるハロゲン含有樹脂の無害化処理方法に関する。
【００２６】
テレビやラジカセ、卓上コンピュータなどの家電製品の筐体には、ＡＢＳ樹脂や耐衝撃性ポリスチレン樹脂が広く使用されている。これらのＡＢＳ樹脂や耐衝撃性ポリスチレン樹脂には、安全上の理由から各種の難燃剤を配合することが一般的に行われている。これらの難燃剤としては、従来は、ハロゲン系難燃剤が広く用いられてきた。しかし、ハロゲン系難燃剤を配合したＡＢＳ樹脂や耐衝撃性ポリスチレン樹脂を単に焼却処分すると、ハロゲン系難燃剤に含まれているハロゲンがＡＢＳ樹脂や耐衝撃性ポリスチレン樹脂と反応してダイオキシンが発生する可能性がある。
【００２７】
請求項９の無害化処理方法によれば、このようなＡＢＳ樹脂や耐衝撃ポリスチレン樹脂に含まれているハロゲンも、塩化ビニル樹脂などのハロゲン化ビニル系樹脂に含まれるハロゲンと同様に、前記石膏類と反応して固定化されるから、ダイオキシンが発生することはない。
【００２８】
請求項７に記載の発明は、前記ハロゲン化ビニル系樹脂は、塩化ビニル系樹脂および塩化ビニリデン系樹脂からなる群から選択された１種以上の樹脂であるハロゲン含有樹脂の無害化処理方法に関する。
【００２９】
請求項１０は、本発明の無害化処理方法が、軟質塩化ビニル樹脂や硬質塩化ビニル樹脂のような塩化ビニル系樹脂、および塩化ビニリデン系樹脂の無害化処理に特に好適に使用されることを明らかにした請求項である。
【００３０】
【発明の実施の形態】
本発明の各構成要素について、以下に詳説する。
【００３１】
本発明の無害化処理方法で処理できるハロゲン含有樹脂としては、前述のハロゲン含有熱可塑性樹脂およびハロゲン含有熱硬化性樹脂が挙げられる。
【００３２】
前記ハロゲン含有熱可塑性樹脂としては、ハロゲン化ビニル系樹脂および難燃化ビニル系樹脂組が挙げられる。
【００３３】
ハロゲン化ビニル系樹脂としては、具体的には、ハロゲン基を有するハロゲン化ビニル化合物の単独重合体および共重合体が挙げられるが、他に、ハロゲン基を有しないビニルモノマーを重合して得られるハロゲン非含有ビニル系樹脂に塩素化などのハロゲン化処理を施したハロゲン化処理樹脂が挙げられる。
【００３４】
前記ハロゲン化ビニル化合物としては、ハロゲン基を１個または２個以上有するビニル化合物が挙げられ、具体的には、塩化ビニル、臭化ビニル、塩化ビニリデン、および臭化ビニリデンなどが挙げられる。
【００３５】
したがって、ハロゲン化ビニル化合物の単独重合体としては、塩化ビニル、臭化ビニル、塩化ビニリデン、および臭化ビニリデンの単独重合体および共重合体が挙げられ、具体的には、ポリ塩化ビニル樹脂、塩化ビニル・高級ビニルエーテル共重合体、塩化ビニル・酢酸ビニル共重合体、塩化ビニル・酢酸ビニル・マレイン酸エステル共重合体、エチレン・塩化ビニル共重合体、エチレン・酢酸ビニル・塩化ビニルグラフト共重合体などの塩化ビニル系樹脂、および塩化ビニリデン・塩化ビニル共重合体樹脂、塩化ビニリデン・アクリロニトリル共重合体、塩化ビニリデン・（メタ）アクリル酸エステル共重合体などの塩化ビニリデン系樹脂などが挙げられる。なお、ポリ塩化ビニル樹脂には、軟質塩化ビニル樹脂も硬質塩化ビニル樹脂も含まれる。また、これらの単独重合体および共重合体は、塩素化処理などのハロゲン化処理を施したものも、本発明の無害化処理方法で処理できる。
【００３６】
前記ハロゲン化処理樹脂としては、ハロゲン化ポリエチレンおよびハロゲン化ポリプロピレンなどが挙げられる。
【００３７】
難燃化ビニル系樹脂としては、ＡＡＳ樹脂、ＡＢＳ樹脂、ＡＥＳ樹脂、ＡＣＳ樹脂、ＭＢＳ樹脂、ＡＳ樹脂、耐衝撃性ポリスチレン樹脂、スチレン・（メタ）アクリル酸エステル共重合体樹脂などにハロゲン系難燃剤を配合したものが挙げられる。
【００３８】
一方、ハロゲン含有熱硬化性樹脂としては、臭素化ビスフェノールＡ型エポキシ樹脂のように、骨格中にハロゲン基を有するエポキシ樹脂が挙げられる。
【００３９】
石膏類としては、たとえば、硫酸カルシウム、結晶石膏、半水石膏、無水石膏、石膏プラスタ、無水石膏プラスタ、および硬石膏プラスタを使用できる。石膏類は、天然石膏および化学石膏の何れも包含する。
【００４０】
ハロゲン含有樹脂と石膏類との反応温度は１５０℃以上であり、１５０℃〜１００℃の範囲が好ましく、特に４００〜８００℃の範囲が好ましい。前記反応温度が１５０℃以上であれば、ハロゲン含有樹脂中のハロゲンと石膏類との反応は充分に進行する。また、反応温度が１０００℃以下であれば、ハロゲン含有樹脂と石膏類との反応によって生じた反応物が再分解してハロゲンが発生することがない。また、後述するように、前記反応を焼却炉で実施する場合においても、炉壁が痛むことが少ない。
【００４１】
ハロゲン含有樹脂と石膏類との割合は、ハロゲン含有樹脂と石膏類との合計量を１００重量部としたとき、石膏類が５〜３０重量部になるようにすることが好ましく、特に石膏類が１０〜２５重量部になるようにすることが好ましい。
【００４２】
ハロゲン含有樹脂と石膏類との反応は、たとえば、ハロゲン含有樹脂と石膏類とを混合して豆炭状、団子状、またはペレット状に形成し、これを通常の焼却炉で焼却すればよい。ハロゲン含有樹脂と石膏類とを混合するときは、ハロゲン含有樹脂を加熱・溶融してその中に石膏類を添加してもよく、また、非揮発性油を配合してハロゲン含有樹脂と石膏類とを固めてもよい。非揮発性油としては、重油、軽油、灯油、機械油、エンジン油、廃油、食用油、廃食用油などの常温で揮発性を有しない油類を使用できる。非揮発性油の割合は、ハロゲン含有樹脂と石膏類との合計量１００重量部に対して５〜５０重量部が好ましく、特に１０〜２０重量部が好ましいが、ハロゲン含有樹脂と石膏類との混合物を均一な豆炭状、団子状、またはペレット状に形成できるのであれば、前記割合には限定されない。
【００４３】
ハロゲン含有樹脂と石膏類とを反応させる方法としては、また、前記ハロゲン含有樹脂を前記非揮発性油に溶解し、これに石膏類を添加して前記反応温度に保持する方法がある。
【００４４】
ハロゲン含有樹脂と石膏類とを反応させる方法としては、更に、石膏類の粒子または粉末を流動床とする流動床型反応装置を用い、前記流動床を所定温度に保持してその中にハロゲン含有樹脂を適当な大きさに粉砕したものを投入して処理する方法がある。
【００４５】
ハロゲン含有樹脂と石膏類との反応時間は、反応温度および反応方法に応じて適宜定めることができる
本発明に係るハロゲン含有樹脂の無害化処理方法の具体的な態様としては、
▲１▼塩化ビニル系樹脂と石膏類とを溶融混合して豆炭状、団子状、またはペレット状に成形し、これを焼却炉で４００〜８００℃の温度で焼却する方法、
▲２▼塩化ビニル系樹脂と石膏類とに非揮発性油を添加して混合し、豆炭状、団子状、またはペレット状に成形したものを焼却炉で４００〜８００℃の温度で焼却する方法、
▲３▼塩化ビニル系樹脂を非揮発性油に溶解し、これに石膏類を添加して１５０℃以上の温度に保持する方法、
▲４▼塩化ビニル系樹脂を非揮発性油に溶解させ、これに石膏類を添加して、燃焼炉中に噴射して燃焼させる方法、
▲５▼石膏類を流動床とする流動床型反応装置中に塩化ビニル系樹脂を投入して反応させる方法
などが挙げられるが、本発明は、これらの態様には限定されない。
【００４６】
【実施例】
（実施例１）
ハロゲン含有樹脂としてビニルハウスに使用された廃軟質塩化ビニル樹脂シートを用い、石膏類として石膏プラスタを用いた。
【００４７】
前記廃軟質塩化ビニル樹脂シートを１〜３ｃｍ角程度の大きさに粉砕したもの８０重量部と石膏プラスタ２０重量部と廃油１０重量部とを溶融して攪拌・混合し、そのままの状態に１２時間保持した後、豆炭状に成形した。
【００４８】
これを、重油バーナー式の焼却炉中で４００〜８００℃の温度で焼却し、排ガスおよび焼却灰中に含まれるダイオキシンの濃度を測定した。排ガスおよび焼却灰中のダイオキシン濃度は、「気相ダイオキシン濃度測定要領」（環境庁大気保全局編）に基づいて測定した。
【００４９】
その結果、排ガス中のダイオキシン濃度は、１×１０-6ｇ／Ｎｍ3（排ガス）であり、焼却灰中のダイオキシン濃度は、４×１０-6ｇ／１ｔｏｎ（焼却残滓）であった。後述する比較例１に基づいた除去率に換算すると、排ガスについては９９．９９９９％であり、焼却灰については９９．９９９６％であった。
【００５０】
（比較例１）
石膏プラスタを添加しなかった以外は、実施例１と同様の手順に従って廃軟質塩化ビニル樹脂シートの焼却処理を行い、排ガスおよび焼却灰に含まれるダイオキシンの濃度を測定した。
【００５１】
その結果、排ガス中のダイオキシン濃度は１ｇ／Ｎｍ3（排ガス）であり、焼却灰中のダイオキシン濃度は、４ｇ／１ｔｏｎ（焼却残滓）であった。
【００５２】
【発明の効果】
以上説明したように、本発明によれば、ハロゲン含有樹脂を、ダイオキシンを発生させることなく、しかも安価に処理できるハロゲン含有樹脂の無害化処理方法が提供される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for detoxifying a halogen-containing resin, and more particularly to a method for detoxifying a halogen-containing resin that can treat a vinyl chloride resin or the like without generating dioxins.
[0002]
[Prior art]
In recent years, a large amount of sheets and garbage bags used in agricultural vinyl houses have been discarded.
[0003]
In these sheets and garbage bags, soft vinyl chloride resin is generally used. However, when vinyl chloride resin such as soft vinyl chloride resin is incinerated as it is, extremely toxic dioxins are generated.
[0004]
Therefore, at present, soft vinyl chloride resin sheets used for agricultural vinyl houses are either stored in warehouses or piled up in vacant land, mountainous land, or agricultural land.
[0005]
[Problems to be solved by the invention]
The present invention has been made to solve the above-mentioned problems, and is capable of detoxifying halogen-containing resins such as used soft vinyl chloride resin sheets that can be processed at low cost without generating dioxins. It aims to provide a method.
[0006]
[Means for Solving the Problems]
The invention according to claim 1 is a halogen-containing resin characterized in that the halogen-containing resin is melted, mixed with only gypsum or only gypsum and non-volatile oil, and incinerated at a temperature of 400 to 800 ° C. It relates to a detoxification treatment method.
[0007]
When a halogen-containing resin such as a vinyl chloride resin is burned in the air, a thermal decomposition causes a halogen atom in the halogen-containing resin, such as a chlorine atom, a carbon atom and a hydrogen atom in the halogen-containing resin, and an oxygen atom in the air. Dioxins are generated from
[0008]
However, in the halogenated resin detoxification method, the halogen-containing resin is heated in the presence of gypsum. Here, since gypsum contains calcium sulfate as a main component, all the halogens in the halogen-containing resin react with the calcium sulfate in the gypsum and are fixed. Therefore, generation of dioxins is prevented.
[0010]
In the halogenated resin detoxification method, the reaction temperature between the halogen-containing resin and gypsum is set in the above temperature range, so that all halogen atoms contained in the halogen-containing resin react with gypsum. Therefore, the dioxin generation prevention effect is particularly high. In addition, since the reaction temperature is relatively low at 800 ° C. or lower, it is preferable in that the incinerator is hardly damaged when it is processed using a normal incinerator.
[0011]
The invention according to claim 2 relates to a method for detoxifying a halogen-containing resin in which the proportion of gypsum is 5 to 30 parts by weight when the total amount of the halogen-containing resin and gypsum is 100 parts by weight.
[0012]
In the method for detoxifying a halogen-containing resin of the present invention, if the proportion of gypsum is 5 parts by weight or more, all halogen atoms in the halogen-containing resin react with gypsum. Moreover, if the ratio of gypsum is 30 weight part or less, a solid residue will not generate in large quantities. The invention according to the claims is based on such knowledge.
[0013]
The invention according to claim 3 is the invention according to claim 1 or 2 , wherein only the halogen-containing resin and gypsum, or only the halogen-containing resin, gypsum and non-volatile oil are mixed and incinerated to react with each other. The present invention relates to a method for detoxifying a halogen-containing resin.
[0014]
The method for detoxifying the halogen-containing resin can be easily carried out, for example, by mixing a halogen-containing resin and gypsum and forming it into a bean charcoal shape and incinerating it in an incinerator.
[0016]
The halogen-containing resin detoxification method is an example of the halogen-containing resin detoxification method according to claim 4, wherein the halogen-containing resin is melted and mixed with gypsum.
[0017]
According to this detoxification treatment method, since the halogen-containing resin and gypsum can be mixed uniformly, generation of dioxins when the halogen-containing resin is treated can be more effectively prevented.
[0018]
Further, the detoxification treatment method can be suitably carried out when the halogen-containing resin is thermoplastic such as vinyl chloride resin.
[0020]
In the detoxification method, if the halogen-containing resin can be uniformly mixed with gypsum, and the halogen-containing resin can be dissolved in the non-volatile oil, the halogen-containing resin needs to be thermally dissolved. Absent. This method can be preferably carried out particularly when the halogen-containing resin is dissolved in a non-volatile oil.
[0021]
The invention according to claim 4 is a halogen-containing resin in which the gypsum is selected from the group consisting of calcium sulfate, crystal gypsum, hemihydrate gypsum, anhydrous gypsum, gypsum plaster, anhydrous gypsum plaster, and anhydrite plaster. It relates to a detoxification treatment method.
[0022]
The crystal gypsum, hemihydrate gypsum, anhydrous gypsum, gypsum plaster, anhydrous gypsum plaster, and anhydrite plaster all contain a considerable amount of calcium oxide as an impurity. Therefore, it is considered that the sulfuric acid produced by the reaction of the halogen in the halogen-containing resin with the calcium sulfate contained in the crystal gypsum or the like is fixed by the reaction with the calcium oxide. Done.
[0023]
The invention according to claim 5 is the halogen-containing resin in which the halogen-containing resin is at least one resin selected from a halogen-containing thermoplastic resin having thermoplasticity and a halogen-containing thermosetting resin having thermosetting properties. It relates to the detoxification processing method.
[0024]
The detoxification treatment method of the present invention is applicable not only to a halogen-containing thermoplastic resin such as a vinyl chloride resin described later, but also to a thermosetting resin such as an epoxy resin containing a halogen atom in the skeleton. Is a claim that clarifies that the above can also be applied.
[0025]
The invention described in claim 6 is a halogenated vinyl resin in which the halogen-containing thermoplastic resin is a homopolymer or copolymer of a halogenated vinyl compound having a halogen group, and a vinyl monomer having no halogen group. The present invention relates to a method for detoxifying a halogen-containing resin which is at least one resin selected from the group consisting of flame-retardant vinyl resins obtained by blending a halogen-free flame retardant with a halogen-free vinyl resin obtained by polymerization. .
[0026]
ABS resins and impact-resistant polystyrene resins are widely used in the housings of home appliances such as televisions, radio cassettes, and desktop computers. These ABS resins and impact-resistant polystyrene resins are generally blended with various flame retardants for safety reasons. Conventionally, halogen-based flame retardants have been widely used as these flame retardants. However, if the ABS resin or impact-resistant polystyrene resin blended with a halogen-based flame retardant is simply incinerated, the halogen contained in the halogen-based flame retardant reacts with the ABS resin or impact-resistant polystyrene resin to generate dioxins. there is a possibility.
[0027]
According to the detoxification method of claim 9, the gypsum is similar to the halogen contained in such ABS resin and impact-resistant polystyrene resin, as well as halogen contained in vinyl halide resins such as vinyl chloride resin. Dioxin is not generated because it is immobilized by reacting with other species.
[0028]
The invention according to claim 7 relates to a detoxifying treatment method for a halogen-containing resin, wherein the vinyl halide resin is at least one resin selected from the group consisting of a vinyl chloride resin and a vinylidene chloride resin.
[0029]
Claim 10 reveals that the detoxification treatment method of the present invention is particularly preferably used for the detoxification treatment of vinyl chloride resins such as soft vinyl chloride resins and hard vinyl chloride resins, and vinylidene chloride resins. It is the claim made into.
[0030]
DETAILED DESCRIPTION OF THE INVENTION
Each component of the present invention will be described in detail below.
[0031]
Examples of the halogen-containing resin that can be treated by the detoxifying treatment method of the present invention include the above-mentioned halogen-containing thermoplastic resins and halogen-containing thermosetting resins.
[0032]
Examples of the halogen-containing thermoplastic resin include a halogenated vinyl resin and a flame retardant vinyl resin group.
[0033]
Specific examples of the vinyl halide resin include homopolymers and copolymers of a halogenated vinyl compound having a halogen group. In addition, it is obtained by polymerizing a vinyl monomer having no halogen group. A halogenated resin obtained by subjecting a halogen-free vinyl resin to a halogenation treatment such as chlorination can be mentioned.
[0034]
Examples of the vinyl halide compound include vinyl compounds having one or more halogen groups, and specific examples include vinyl chloride, vinyl bromide, vinylidene chloride, and vinylidene bromide.
[0035]
Therefore, homopolymers of vinyl halide compounds include vinyl chloride, vinyl bromide, vinylidene chloride, and vinylidene bromide homopolymers and copolymers, specifically, polyvinyl chloride resin, chloride Vinyl / higher vinyl ether copolymer, vinyl chloride / vinyl acetate copolymer, vinyl chloride / vinyl acetate / maleic acid ester copolymer, ethylene / vinyl chloride copolymer, ethylene / vinyl acetate / vinyl chloride graft copolymer, etc. And vinylidene chloride resins such as vinylidene chloride / vinyl chloride copolymer resins, vinylidene chloride / acrylonitrile copolymers, vinylidene chloride / (meth) acrylic acid ester copolymers, and the like. The polyvinyl chloride resin includes a soft vinyl chloride resin and a hard vinyl chloride resin. Further, those homopolymers and copolymers that have been subjected to a halogenation treatment such as a chlorination treatment can be treated by the detoxification treatment method of the present invention.
[0036]
Examples of the halogenated resin include halogenated polyethylene and halogenated polypropylene.
[0037]
Flame retardant vinyl resins include AAS resins, ABS resins, AES resins, ACS resins, MBS resins, AS resins, impact-resistant polystyrene resins, styrene / (meth) acrylate ester copolymer resins, and other halogen-based flame retardant resins. What mixed the flame retardant is mentioned.
[0038]
On the other hand, examples of the halogen-containing thermosetting resin include an epoxy resin having a halogen group in the skeleton, such as a brominated bisphenol A type epoxy resin.
[0039]
As the gypsum, for example, calcium sulfate, crystal gypsum, hemihydrate gypsum, anhydrous gypsum, gypsum plaster, anhydrous gypsum plaster, and anhydrite plaster can be used. The gypsum includes both natural gypsum and chemical gypsum.
[0040]
The reaction temperature between the halogen-containing resin and gypsum is 150 ° C or higher, preferably in the range of 150 ° C to 100 ° C, and particularly preferably in the range of 400 to 800 ° C. When the reaction temperature is 150 ° C. or higher, the reaction between the halogen in the halogen-containing resin and gypsum proceeds sufficiently. In addition, when the reaction temperature is 1000 ° C. or less, the reaction product generated by the reaction between the halogen-containing resin and gypsum is not decomposed again to generate halogen. As will be described later, even when the reaction is carried out in an incinerator, the furnace wall is less likely to hurt.
[0041]
The ratio of the halogen-containing resin and the gypsum is preferably 5 to 30 parts by weight when the total amount of the halogen-containing resin and the gypsum is 100 parts by weight. The amount is preferably 10 to 25 parts by weight.
[0042]
The reaction between the halogen-containing resin and gypsum may be, for example, mixing the halogen-containing resin and gypsum to form bean charcoal, dumpling, or pellets, and incinerating them in a normal incinerator. When mixing the halogen-containing resin and gypsum, the halogen-containing resin may be heated and melted, and gypsum may be added to it. Also, a non-volatile oil may be added to mix the halogen-containing resin and gypsum. And may be hardened. Nonvolatile oils such as heavy oil, light oil, kerosene, machine oil, engine oil, waste oil, edible oil, and waste edible oil can be used. The proportion of the non-volatile oil is preferably 5 to 50 parts by weight, particularly preferably 10 to 20 parts by weight with respect to 100 parts by weight of the total amount of the halogen-containing resin and gypsum. The ratio is not limited as long as the mixture can be formed into a uniform bean charcoal, dumpling, or pellet.
[0043]
As a method of reacting the halogen-containing resin and gypsum, there is also a method in which the halogen-containing resin is dissolved in the non-volatile oil, and gypsum is added thereto to maintain the reaction temperature.
[0044]
As a method for reacting the halogen-containing resin and gypsum, a fluidized bed type reaction apparatus using a gypsum particle or powder as a fluidized bed is used. The fluidized bed is maintained at a predetermined temperature and contains a halogen. There is a method in which a resin is pulverized to an appropriate size and processed.
[0045]
The reaction time of the halogen-containing resin and gypsum can be appropriately determined according to the reaction temperature and the reaction method, as a specific embodiment of the detoxification treatment method of the halogen-containing resin according to the present invention,
(1) A method in which a vinyl chloride resin and gypsum are melt mixed and formed into a bean charcoal, dumpling, or pellet form, and incinerated at a temperature of 400 to 800 ° C. in an incinerator.
(2) A method in which a non-volatile oil is added to and mixed with a vinyl chloride resin and gypsum, and then molded into a bean charcoal, dumpling or pellet form, and incinerated at a temperature of 400 to 800 ° C. in an incinerator ,
(3) A method in which a vinyl chloride resin is dissolved in a non-volatile oil, gypsum is added to the resin, and the temperature is maintained at 150 ° C. or higher.
(4) A method in which a vinyl chloride resin is dissolved in a non-volatile oil, gypsum is added thereto, and the mixture is injected into a combustion furnace and burned.
{Circle around (5)} Examples include a method in which a vinyl chloride resin is introduced into a fluidized bed reactor using gypsum as a fluidized bed, and the reaction is performed, but the present invention is not limited to these embodiments.
[0046]
【Example】
(Example 1)
The waste soft vinyl chloride resin sheet used in the vinyl house was used as the halogen-containing resin, and gypsum plaster was used as the gypsum.
[0047]
80 parts by weight of the waste soft vinyl chloride resin sheet pulverized to a size of about 1 to 3 cm square, 20 parts by weight of gypsum plaster and 10 parts by weight of waste oil are melted, stirred and mixed, and left as it is for 12 hours. After holding, it was shaped into a bean charcoal shape.
[0048]
This was incinerated at a temperature of 400 to 800 ° C. in a heavy oil burner type incinerator, and the concentration of dioxin contained in the exhaust gas and incinerated ash was measured. Dioxin concentration in exhaust gas and incineration ash was measured based on “Guideline for Measuring Gas Phase Dioxin Concentration” (Edited by the Environmental Protection Agency, Environment Agency).
[0049]
As a result, the dioxin concentration in the exhaust gas was 1 × 10 −6 g / Nm 3 (exhaust gas), and the dioxin concentration in the incineration ash was 4 × 10 −6 g / 1 ton (incineration residue). When converted to a removal rate based on Comparative Example 1 described later, the exhaust gas was 99.9999% and the incinerated ash was 99.999%.
[0050]
(Comparative Example 1)
Except for not adding gypsum plaster, the waste soft vinyl chloride resin sheet was incinerated according to the same procedure as in Example 1, and the concentration of dioxin contained in the exhaust gas and incinerated ash was measured.
[0051]
As a result, the dioxin concentration in the exhaust gas was 1 g / Nm 3 (exhaust gas), and the dioxin concentration in the incineration ash was 4 g / 1 ton (incineration residue).
[0052]
【The invention's effect】
As described above, according to the present invention, there is provided a harmless treatment method for a halogen-containing resin that can treat the halogen-containing resin at low cost without generating dioxins.
Claims (6)
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